Optical resin composition and method for producing the same

ABSTRACT

To provide an optical resin composition containing carbonate crystals, which have oriented birefringence, have a needle- or rod-like shape, and are able to negate the birefringence without sacrificing the light transmittance of a transparent polymeric resin where the carbonate crystal exists, and a method for producing the resin composition. To achieve this provided are an optical resin composition containing a resin and carbonate crystals, wherein the carbonate crystals have a specific surface area of 4 m 2 /g or more, and the carbonate crystals dispersed into the resin have an average dispersion diameter of 500 nm at a maximum, and a method for producing the optical resin composition.

TECHNICAL FIELD

The present invention relates to an optical resin composition containingcarbonate crystals which have oriented birefringence, have a needle- orrod-like shape and are able to negate the birefringence withoutsacrificing the light transmittance of a transparent resin where thecarbonate crystal exists, and a method for producing the optical resincomposition.

BACKGROUND ART

Carbonates such as calcium carbonate have long been widely used in areassuch as rubber, plastics and papermaking. Recently, many types ofcarbonates with high functionality have been developed and put intopractical use for a variety of applications and purposes according toparticle shapes and diameters.

Examples of crystal forms of the carbonates include calcite, aragoniteand vaterite. Of these, the aragonite is needle-like and has superiorhardness and coefficient of elasticity, and it may be used for versatileapplications.

Commonly known methods for producing the carbonates are, for example:(1) a reaction of a solution containing carbonate ions with a chloridesolution, and (2) a reaction of chloride with carbon dioxide. Also,Patent Literature 1 proposes a method regarding the method (1) toproduce a needle-like carbonate having aragonite structure, wherein areaction of a solution containing carbonate ions with a chloridesolution takes place under ultrasonic irradiation. However, thecarbonate obtained by the production method described in PatentLiterature 1 is not only oversized of 30 μm to 60 μm in length but alsohas a wide distribution in the particle size; a carbonate controlled fora desired particle size may not be obtained.

In addition, regarding a method of introducing carbon dioxide into waterslurry of Ca(OH)₂, Patent Literature 2 proposes a method to place a seedcrystal of needle-like aragonite in Ca(OH)₂ water slurry and grow theseed crystal only in a certain direction. Furthermore, there is aproblem that only a large particle of 20 μm to 30 μm in length may beobtained even with the method for producing a carbonate described inPatent Literature 2.

On the other hand, in recent years, the majority of optical-glassproducts such as glass lens and camera lens have been replaced bypolymeric optical materials in view of their lightness, easy processing,superior mass productivity, and simplicity in application of moldingtechnologies such as injection molding and extrusion molding. Formaterials of optical components for opto-electronics, especially foroptical components used for laser-related devices such as optical discdevices for recording sounds, images, literal information and the like,there is a strong tendency to use polymeric materials.

A polymeric material having birefringence does not cause a problem whenit is applied to optical components which do not require relatively highprecision. However, optical components requiring higher precision havebeen demanded recently, and birefringence is a big issue in case of, forexample, a writable/erasable magneto-optical disc. Birefringence is aproperty that a light beam passing through a certain substance isseparated into two light beams depending on the conditions of polarizedlight beams. Birefringence index is given as the difference inrefractive index between the directions of the polarized lights in thesubstance.

However, there is a problem that an optical component obtained bymolding the common polymeric materials exhibits birefringence. Asemiconductor laser beam is used for reading and writing this kind ofmagneto-optical disc; the existence of an optical component withbirefringence in the disc itself or in the lens, for example, on thelight path may adversely affect the precision in reading or writing.

Given this factor, Patent Literature 3 proposes a non-birefringentoptical resin material containing a polymeric resin and an inorganicfine particle having different signs of birefringence for the purpose ofreducing the birefringence. The non-birefringent optical resin materialof this proposal is obtained by a method called crystal doping, wherein,for example, a number of inorganic fine particles are dispersed in apolymeric resin, and the bonding chains in the polymeric resin and theinorganic fine particles are oriented in an approximately paralleldirection by externally applying a molding force such as drawing so asto diminish the birefringence caused by the orientation of the bondingchain in the polymeric resin with the birefringence of the inorganicfine particles having an opposite sign.

As stated above, inorganic fine particles that may be used for a crystaldoping is essential in order to obtain a non-birefringent optical resinmaterial through the crystal doping. The inorganic fine particles arerequired to have a shape with a high aspect ratio such as a needle- orrod-like shape to align the carbonate particles along the orientation ofthe bonding chain in the polymeric resin. Carbonate particles which donot influence a light transmittance, which is an important function asan optical material, is demanded. In addition, the average particle sizeof carbonate crystals need to be sufficiently small compared to thewavelength of a light source to reduce the effect of light scattering byparticles as much as possible so that it does not affect the lighttransmittance.

However, it is difficult to disperse carbonate crystals in a resinwithout causing flocculation, and merely designing individual carbonatecrystal particles to have a desired form or size is not necessarilysatisfactory. Therefore, development of a technology for preventingdecrease in transmittance of the optical resin material caused by theflocculation of carbonate crystal particles is highly demanded.

Patent Literature 1 Japanese Patent Application. Laid-Open (JP-A) No.59-203728

Patent Literature 2 U.S. Pat. No. 5,164,172

Patent Literature 3 International Publication WO No. 01/25364

DISCLOSURE OF INVENTION

An object of the present invention aims to solve the conventionalproblems and achieve the following objects. Specifically, the object ofthe present invention is to provide an optical resin compositioncontaining a carbonate crystal (hereinafter may be referred to as“carbonate particle” or “carbonate crystal particle”), which hasoriented birefringence, is needle- or rod-like, and is able to negatethe birefringence without sacrificing the light transmittance of atransparent polymeric resin where the carbonate crystal exists, and amethod for producing the optical resin composition.

In view of the above-mentioned shortcomings, the inventors of thepresent invention have conducted extensive studies and established thatin order for resin to keep high transparency, it is critical thatcarbonate crystal fine particles having a specific surface area of 4m²/g or more be taken out beforehand as a dry powder with no flocculatedparticles by removing adsorbates from the particle surfaces prior toaddition into resin, and then the carbonate crystal fine particles aredispersed into the resin, whereby an optical resin composition can beobtained that negates birefringence without sacrificing lighttransmittance.

The present invention is based on the findings of the inventors, and themeans for solving the problem is as follows:

<1> An optical resin composition containing a resin and carbonatecrystals having a specific surface area of 4 m²/g or more, wherein thecarbonate crystals dispersed into the resin have an average dispersiondiameter of 500 nm at a maximum.<2> The optical resin composition according to <1>, wherein the opticalresin composition has a light transmittance of 86% or greater at awavelength of 450 nm.<3> The optical resin composition according to any one of <1> and <2>,wherein the content of the carbonate crystals relative to the resin is0.01% by mass to 15.00% by mass.<4> The optical resin composition according to any one of <1> to <3>,wherein the resin is any one selected from a cellulose acylate resin, apolyethylene terephthalate resin, a polyethylene naphthalate resin and apolycarbonate resin.<5> The optical resin composition according to any one of <1> to <4>,wherein the optical resin composition is used in a drawn film.<6> The optical resin composition according to any one of <1> to <5>,wherein the carbonate crystals have an aspect ratio of 2 or greater, anaverage major axis length of 400 nm or shorter, and a variationcoefficient of the major axis expressed by Formula (1) of 0.40 or less:

$\begin{matrix}{\frac{1}{r} \times \left\{ {\frac{1}{n - 1}{\sum\limits_{i = 1}^{n}\left( {r_{i} - r} \right)^{2}}} \right\}^{\frac{1}{2}}} & {{Formula}\mspace{14mu} (1)}\end{matrix}$

wherein r denotes an average major axis length, n denotes the number ofparticles whose major axis length is measured, and r_(i) denotes themajor axis length of the i^(th) particle measured.

<7> The optical resin composition according to any one of <1> to <6>,wherein the carbonate crystals are produced by reacting a metal ionsource containing at least one metal ion selected from Sr²⁺, Ca²⁺, Ba²⁺,Zn²⁺ and Pb²⁺ with a carbonate source in liquid.<8> The optical resin composition according to <7>, wherein thecarbonate crystals are produced by the method including increasing, atleast once, the number of the carbonate crystals in liquid, andincreasing, at least once, only the volume of the carbonate crystals inliquid.<9> The optical resin composition according to any one of <7> to <8>,wherein the optical resin composition is formed by reacting the metalion source with the carbonate source in liquid by a single-jet method.<10> The optical resin composition according to any one of <1> to <9>,wherein the optical resin composition is used in an optical element.<11> The optical resin composition according to <10>, wherein theoptical element is a magneto-optical disc.<12> A method for producing an optical resin composition including:producing carbonate crystals, and dispersing the produced carbonatecrystals into a resin, wherein the step of producing carbonate crystalsincludes reacting a metal ion source containing at least one metal ionselected from Sr²⁺, Ca²⁺, Ba²⁺, Zn²⁺ and Pb²⁺ with a carbonate source inliquid.<13> The method for producing an optical resin composition according to<12>, wherein the carbonate crystals have a specific surface area of 4m²/g or more, and the carbonate crystals dispersed into the resin havean average dispersion diameter of 500 nm at a maximum.<14> The method for producing an optical resin composition according toany one of <11> to <13>, wherein the step of producing carbonatecrystals includes removing an adsorbate from surfaces of the carbonatecrystals.<15> The method for producing an optical resin composition according to<14>, wherein the step of removing an adsorbate includes any one of amethod for washing the carbonate crystal at least once by decantationand a method for subjecting the carbonate crystal to ultrafiltration atleast once.<16> The method for producing an optical resin composition according to<15>, wherein a supernatant obtained by decantation or a filtrateobtained by the ultrafiltration has a conductivity of 100 μS/cm or less.<17> The method for producing an optical resin composition according toany one of <12> to <16>, wherein the step of producing carbonatecrystals includes increasing, at least once, the number of the carbonatecrystal in liquid, and increasing, at least once, only the volume of thecarbonate crystals in liquid.<18> The method for producing an optical resin composition according toany one of <12> to <17>, wherein the step of producing carbonatecrystals includes reacting the metal ion source with the carbonatesource in liquid by a single-jet method.<19> The method for producing an optical resin composition according toany one of <12> to <18>, wherein the temperature of the step ofincreasing the number of the carbonate crystals is −10° C. to 40° C.,and a temperature of the step of increasing the volume of the carbonatecrystal is 1° C. to 60° C. and not less than the temperature of the stepincreasing the number of the carbonate particles.<20> The method for producing an optical resin composition according to<12>, wherein the step of dispersing the carbonate crystals into theresin includes dispersing the carbonate crystal into the resin bykneading.<21> The method for producing an optical resin composition according to<12>, wherein in the step of dispersing the carbonate crystal into theresin the carbonate crystals are added into the resin at least beforecompletion of the polymerization reaction for the preparation of theresin.<22> The method for producing an optical resin composition according toany one of <20> and <21>, wherein a method for molding the optical resincomposition in which the carbonate crystal is dispersed is any one of aninjection molding, press molding and extrusion molding.<23> The method for producing an optical resin composition according to<22>, wherein the optical resin composition obtained by the injectionmolding, press molding and extrusion molding is drawn so as to form afilm.

The present invention can solve the conventional problems and provide anoptical resin composition containing a carbonate crystal which hasoriented birefringence, is needle- or rod-like and is able to negate thebirefringence without sacrificing light transmittance of a transparentpolymeric resin where the carbonate crystal exists, and a method forproducing the optical resin composition.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a process drawing illustrating an example of process ofproducing carbonate crystals by means of a double jet method in themethod for producing an optical resin composition of the presentinvention.

FIG. 2 is a process drawing illustrating an example of process ofproducing a carbonate crystal by means of a single-jet method in themethod for producing an optical resin composition of the presentinvention.

BEST MODE FOR CARRYING OUT THE INVENTION Optical Resin Composition

An optical resin composition of the present invention contains acarbonate crystal in the invention dispersed into a resin, andoptionally other components.

—Carbonate Crystal—

The carbonate crystals can be obtained by reacting a metal ion sourcewith a carbonate source in liquid, and their specific surface area,aspect ratio, average major axis length and variations in the major axisfall within respective predetermined ranges. The carbonate crystal isadded to resin for use and has a relative value for light transmittanceat a wavelength of 450 nm of not less than a predetermined value.

—Metal Ion—

The metal ion source is not particularly limited and may be suitablyselected in accordance with the intended use as long as it contains ametal ion. Examples of the metal ion sources include Sr²⁺ ion, Ca²⁺ ion,Ba²⁺ ion, Zn²⁺ ion and Pb²⁺ ion. Of these, Sr²⁺ ion, Ca²⁺ ion, and Ba²⁺ion, each of which is an alkali earth metal ion, are particularlypreferable from the perspective of reactivity. A metal ion sourcecapable of reacting with a carbonate source and forming a carbonatehaving any one of crystal forms of calcite, aragonite, vaterite, andamorphous is preferable, and a metal source capable of forming acarbonate having an aragonite crystal structure is particularlypreferable.

The aragonite crystal structure is represented by CO₃ ²⁻ unit, aplurality of the CO₃ ²⁻ unit are formed in a laminate structure to forma carbonate crystal having a needle-like shape or a rod-like shape.Thus, anisotropy arises in the crystal structure, the refractive indexvaries depending on the axial direction of the crystal, and the crystalresults in a biaxial and negative optical crystal. Table 1 showsrespective refractive indexes of crystals in each of crystal axialdirections of carbonates of which the metal ion is Ca²⁺, Sr²⁺, Ba²⁺, orPb²⁺ in carbonate particles. For the reason, the carbonate is drawn inarbitrarily determined one direction by a drawing process, which will bedescribed below, and crystal molecules are arrayed in a state where themajor axis direction of the particles corresponds to the drawingdirection. Thus, the orientation birefringence of the resin can becontrolled by mixing the resin to a resin having a positively orientatedbirefringence.

TABLE 1 Specific α β γ δ gravity CaCO³ 1.530 1.681 1.685 0.155 2.94SrCO³ 1.520 1.667 1.669 0.149 3.75 BaCO³ 1.529 1.676 1.677 0.148 4.29PbCO³ 1.804 2.076 2.078 0.274 6.55

The metal ion source is not particularly limited and may be suitablyselected in accordance with the intended use as long as it contains Sr²⁺ion, Ca²⁺ ion, Ba²⁺ ion, Zn²⁺ ion, and Pb²⁺ ion and examples thereofinclude at least one of nitrate salts, chlorides, and hydroxidesselected from Sr, Ca, Ba, Zn, and Pb. Of these, hydroxides and chloridesare particularly preferable from the perspective of reactivity.

Preferably, the metal ion source contains at least any one of NO₃ ⁻,Cl⁻, and OH⁻. Specifically, examples of the metal ion sources include Sr(NO₃)₂, Ca(NO₃)₂, Ba(NO₃)₂, Zn(No₃)₂, Pb(No₃)₂, SrCl₂, CaCl₂, BaCl₂,ZnCl₂, PbCl₂, Sr(OH)₂, Ca(OH)₂, Ba(OH)₂, Zn(OH)₂, Pb(OH)₂, and hydratesthereof.

—Carbonate Source—

The carbonate source is not particularly limited and may be suitablyselected in accordance with the intended use as long as it generates CO₃²⁻ ion. Examples thereof include sodium carbonate [Na₂CO₃], sodiumhydrogen carbonate [NaHCO₃], carbon dioxide gas and urea [(NH₂)₂CO]. Ofthese, sodium carbonate, ammonium carbonate, and carbon dioxide gas areparticularly preferable from the perspective of reactivity.

—Specific Surface Area, Aspect Ratio, Average Major Axis Length andVariation in Major Axis—

It is required that the specific surface area of the carbonate crystalparticles or surface treated carbonate crystal particles, as measuredprior to addition to resin, be 4 m²/g or more, more preferably 6 m²/g ormore, and particularly preferably 8 m²/g or more. When the specific areais less than 4 m²/g, it is often the case that the crystal carbonateparticles have already flocculated at the time of producing the crystalcarbonate, and even when the crystal carbonate is added to and dispersedinto the resin, the flocculated crystal carbonate is further flocculatedto cause a greater size of aggregate, resulting in significant decreasein light transmittance.

The specific surface area of the crystal carbonate can be measured usinga commercially available nitrogen-adsorption apparatus. For example, thespecific surface area can be measured using an automatic specificsurface area/micropore distribution analyzer (BELSORP-mini, manufacturedby BEL JAPAN Inc.).

The aspect ratio of the carbonate particle is required to be 2 or more,preferably 3 to 20, and particularly preferably 3 to 8.

When the aspect ratio is less than two, the shape of the carbonatecrystal is closer to a granulated shape or a spherical shape, theoccurrence of the particle orientation along the molecular orientationof the transparent resin becomes less probable, or it does not occur atall. Consequently, the present invention becomes ineffective. When theaspect ratio of the carbonate particle is more than 20, the carbonateparticles are destructed in the course of producing the optical resincomposition, and resultingly, the major axis direction of the carbonateparticle may not be aligned in one direction, although the presentinvention relates to a technique of compensating orientationbirefringence associated with molecular orientation by making theorientation of molecules develop in accordance with the molecularorientation of the transparent resin.

The average of the major axis length which is the maximum length of aneedle- or rod-like shaped carbonate crystal along its long axisdirection is preferably shorter than the wavelength of visible light(approximately 400 nm to 780 nm) in order to suppress the decrease intransmittance of the transparent optical resin as much as possible.Therefore, the average major axis length of the carbonate crystal shouldbe 400 nm or shorter. It is preferably 300 nm or shorter, and morepreferably 200 nm or shorter. The effect of Mie scattering by particlesincreases when the average major axis length is longer than 400 nm. Thisaccelerates the decrease in the light transmittance, and the materialloses its value as a transparent optical material.

Regarding the variation in the major axis, the variation coefficient ofthe major axis should be 0.40 or less in order to reduce the content ofthe particles that cause transmittance reduction by light scattering andthereby to achieve a practically low light-scattering status. Thevariation coefficient of a major axis is expressed as a ratio of thestandard deviation of the major axis to the average major axis length,and it may be obtained from Formula (1):

$\begin{matrix}{\frac{1}{r} \times \left\{ {\frac{1}{n - 1}{\sum\limits_{i = 1}^{n}\left( {r_{i} - r} \right)^{2}}} \right\}^{\frac{1}{2}}} & {{Formula}\mspace{14mu} (1)}\end{matrix}$

where r denotes the average major axis length, n the number of particlesused for measurement of the major axis length, and r_(i) the major axislength of the i^(th) particle measured.

The value of n is preferably large. Although it is set at 100 orgreater, the value of n is more preferably 200 or greater. The particledistribution may not be accurately represented with the value of n lessthan 100. When the variation coefficient is expressed in percentage, thevalue obtained from Formula (1) is multiplied by 100. For example, thevariation coefficient of 0.40 or less may be expressed as the variationcoefficient of 40% or less.

The variation coefficient of the major axis is preferably small. Morespecifically, it is preferably 0.30 or less, and more preferably 0.20 orless. The variation coefficient of the major axis of greater than 0.40increases the proportion of particles having a major axis of longer thanthe average major axis length, and the light transmittance in the resinmay be decreased.

The each method of measuring the major axis length, aspect ratio,variation coefficient and the like of the carbonate crystal is notparticularly limited and may be suitably selected in accordance with theintended use. For example, adequately dispersed carbonate particles areobserved through the use of a transmission electron microscope (TEM);the shot image of particles is scanned and stored as an image file; theimage file information is opened with Mac-View Ver. 3, a particle sizedistribution analysis software manufactured by Mountech Co., Ltd., andeach of the particles is measured; and finally the results arecalculated.

—Dispersion Diameter and Dispersion Content—

A dispersion diameter means the average of maximum long axis lengths ofindividual dispersed particles, and also encompasses the dispersiondiameters of primary particles, secondary particles, lattice-shapedparticles, chain-linked particles, and amorphous cubic particles. Whenan average dispersion diameter is defined as an average size of thecarbonate crystal particles actually residing in the resin after thecarbonate crystal particles are mixed with the resin by kneading or thelike, the average dispersion diameter of the carbonate crystal particlesdispersed into the resin is preferably 500 nm at a maximum, morepreferably 450 nm or less, and particularly preferably 400 nm or less.When the average dispersion diameter is greater than 500 nm, thetransparency of the resin containing the carbonate crystals may besignificantly decreased. The average dispersion diameter of thecarbonate crystals can be determined by observing the carbonate crystalsresiding in the resin using a scanning electron microscope (SEM); theshot image of the particles is scanned and stored as an image file; theimage file information is opened with Mac-View Ver. 3, a particle sizedistribution analysis software manufactured by Mountech Co., Ltd., andthe maximum major axis length of each particle is measured; and finallythe results are averaged.

The content of the carbonate crystal relative to the resin is preferably0.01% by mass to 15.00% by mass, more preferably 0.05% by mass to 3.00%by mass, and particularly preferably 0.10% by mass to 2.00% by mass.When the content of the carbonate crystal is less than 0.01% by mass, aneffect of controlling birefringence by adding the particles may not beexerted. When the content of the carbonate crystal is more than 15.00%by mass, the optical resin composition has an effect of controllingbirefringence, but may not keep necessary transparency.

—Resin—

The resin is not particularly limited and may be suitably selected inaccordance with the intended use as long as it is generally used inoptical components, and has a certain degree of transparency. Examplesof the resins include polyolefins such as polyethylene andpolypropylene; aromatic vinyl polymers such as polystyrene; apoly(meth)acrylic esters such as polymethylmethacrylate; polyphenyleneoxide, polycarbonate, polyvinyl chloride, polyethylene terephthalate,polyethylene naphthalate, cyclohexyl methacrylate, cellulose acylate,alicyclic polyolefin (for example, a cyclic olefin ring-opening polymeror copolymer such as norbornene polyolefin); and a copolymer ofalicyclic(meth)acrylate such as isobornyl methacrylate and(meth)acrylphenylene ether. Of these, the polyethylene terephthalate,the polyethylene naphthalate, the cellulose acylate and thepolycarbonate as a resin having preferable optical and physicalproperties, and the polycarbonate is most preferable since itsufficiently develops an advantageous effect of the present inventioneven with an incident light in an oblique direction.

—Light Transmittance at Wavelength of 450 nm—

The light transmittance at a wavelength of 450 nm is preferably 86% ormore in the optical resin composition in which the carbonate crystal isadded to the resin, more preferably 86.5% or more, and particularlypreferably 87% or more. When the light transmittance is less than 86%,the transparency of the resin is lowered and then the opticalinformation may be decreased.

When the film thickness of the resin is set at 100 μm, the lighttransmittance at a wavelength of 450 nm in the resin before thecarbonate crystal being added thereto is taken as x %, and the lighttransmittance at a wavelength of 450 nm in the resin after the carbonatecrystal being added thereto is taken as y %, the value y/x is preferably0.98 or more, particularly preferably 0.99 or more, and 1 is the mostpreferable. When the value y/x is less than 0.98, the transparency ofthe resin to which the carbonate crystal is added may be impaired.

—Application—

The characteristic birefringence values of resins containingbirefringence have been documented, for example, by Fumio Ide on page 29of “Contemporary transparent resins—the world of high-performanceoptical material for challenging IT—” (Kogyo Chosakai Publishing, Inc.;first edition), and are listed in Table 2. Table 2 indicates that themost of the resins contain positive birefringence. Also, when strontiumcarbonate particles with a shape having a high aspect ratio such as aneedle- or rod-like shape are employed as the carbonate and added forexample to polycarbonate used as the optical polymer followed by drawingof the polycarbonate, the carbonate particles align along theorientation of the polymer molecules For example, Yasuhiro Koike andTagaya Akihiro “Polymer and Advanced Materials One Point 1 PhotonicsPolymer” (KYORITSU SHUPPAN Co., Ltd.; first edition) discloses thatselection of inorganic crystals having a high aspect ratio andbirefringence whose sign is opposite to the sign of the birefringence ofthe polymer in the aligned state leads to cancellation of birefringence.Thus, it is made possible not only to exactly cancel birefringence, butalso to make the relative birefringence negative. Therefore, thecarbonate crystals may be suitably employed for optical components, andmore preferably resins make up optical elements in which thebirefringent properties is important and high precision is required.

TABLE 2 Polymer Birefringence Polystyrene −0.10 Polyphenylene ether 0.21Polycarbonate 0.106 Polyvinyl chloride 0.027 Polymethylmethacrylate−0.0043 Polyethylene terephthalate 0.105 Polyethylene 0.044

(Method for Producing Optical Resin Composition)

The method for producing the optical resin composition includes aprocess of producing a carbonate crystal, and a process of dispersingthe produced carbonate crystal into a resin, and further includes otherprocesses in accordance with the necessity.

—Process of Producing Carbonate Crystal—

A process of producing a carbonate crystal includes a treatment ofreacting the metal ion source with the carbonate source in liquid so asto obtain a carbonate crystal, and a treatment of removing an adsorbatefrom a carbonate crystal surface (hereinafter may be simply referred toas an adsorbate removal treatment), and further includes othertreatments in accordance with the necessity. In the treatment ofreacting the metal ion source with the carbonate source in liquid so asto obtain carbonate crystals, a treatment of increasing the number ofcarbonate particles and a treatment of increasing only the volume ofcarbonate particles (hereinafter may be simply referred to as volumeincreasing treatment) may be separately performed.

—Reaction Method—

The method of reacting the metal ion source with the carbonate source inliquid is not particularly limited and may be suitably selected inaccordance with the intended use, for example, a method in which themetal ion source and the carbonate source are added in liquid at thesame time to react them, from the perspective of reactivity. Examples ofthe methods include a double-jet method and a single-jet method. Toobtain a carbonate crystal in the invention, both methods can be used,however, when a metal hydroxide is used as the metal ion source, thesingle-jet method is preferably used. Further, specifically, when asolvent used in the reaction contains water, the concentration of ametal hydroxide is increased because of the metal hydroxide having a lowsolubility to water. Thus, all the metal hydroxide is not dissolved inwater and forms suspension. Then, the suspension is left at rest, theundissolved metal hydroxide is settled out. In most cases, a rawmaterial tank used for the double-jet method or single-jet method is notequipped with a stirring equipment, and therefore, it is unfavorablethat a suspension is poured into the raw material tank. It is mostpreferable that the metal hydroxide suspension is previously put in areaction vessel equipped with stirring blades, and the carbonate sourceis preferably added in the suspension using a nozzle. Thus, thesingle-jet method is preferably used.

—Double Jet Method—

In the double-jet method, the metal ion source and the carbonate sourceare respectively added on surfaces of individual reaction liquids or inindividual liquids by spraying to react them. For example, as shown inFIG. 1, a liquid containing the metal ion source (Liquid A) and a liquidcontaining the carbonate source (Liquid B) are sprayed in Liquid C atthe same time to react the metal ion source and the carbonate source inLiquid C.

The addition rate of the metal ion source and the carbonate source bythe double-jet method is not particularly limited and may be suitablyadjusted in accordance with the intended use. Further, it is preferableto determine the molar addition rate such that the final product cantake the stoichiometric mixture ratio. In the present invention, anequimolar addition rate is most preferable. When the treatment ofincreasing the number of the carbonate particle and the treatment ofincreasing the volume of the carbonate particle are separately performedin the course of forming the final product, the addition rate and thereaction temperature used in each treatment are sometimes varied.

The double-jet method can be carried out using, for example, adouble-jet reactive crystallization apparatus disclosed in JapanesePatent Application Laid-Open (JP-A) No. 05-107668. The apparatusincludes a reaction vessel, stirring blades equipped in the reactionvessel and near the stirring blades provided with two or more nozzlesfor supplying raw material solutions. The metal ion source (Liquid A)supplied from a nozzle and the carbonate source (Liquid B) supplied fromanother nozzle are mixed in an uniform state at a high speed by thestirring blades, and it is possible to uniformly mix and react the bothliquids in Liquid C in a moment of time.

The stirring rate in the double-jet method is preferably 500 rpm to1,500 rpm from the perspective of uniformizing concentrationdistributions of the reaction system, which continuously vary.

—Single-Jet Method—

In the single-jet method, any one of the metal ion source and thecarbonate source is added on the liquid surface of the other source orin the other source liquid by spraying to react them.

The single-jet method can also be performed using the above-noteddouble-jet reactive crystallization apparatus. However, the single-jetmethod requires only one nozzle. For example, as shown in FIG. 2, acarbonate source (Liquid B) sprayed from a nozzle is added to a metalion source (Liquid A) in a tank, thereby the metal ion source can bereacted with the carbonate source just as in the double-jet method.

The addition rate of the metal ion source and the carbonate source, andthe stirring rate in the single-jet method are not particularly limitedand may be suitably selected in accordance with the intended use,however, the addition rate and the stirring rate in the single-jetmethod are preferably within the same range as those in the double-jetmethod. In the single-jet method, when the treatment of increasing thenumber of the carbonate particle and the treatment of increasing thevolume of the carbonate particle are separately performed, in the courseof forming the final product, the addition rate and the reactiontemperature used in each treatment may also be varied.

—Treatment of Increasing the Number of Carbonate Particle—

The treatment of increasing the number of the carbonate particle is notparticularly limited and may be suitably selected in accordance with theintended use as long as the number of a carbonate particle can beincreased after formation of carbonate. Examples thereof include amethod in which any one of a metal ion source and a carbonate source isadded to and mixed with a liquid of which a reaction temperature is setat a given temperature.

Examples of the methods using the single-jet method include a method inwhich an aqueous solution containing the carbonate source is added at agiven addition rate and then mixed to either an aqueous solutioncontaining the metal ion source or a suspension containing the metal ionsource while maintaining the aqueous solution or the suspension at agiven reaction temperature.

The reaction temperature is preferably −10° C. to 40° C., and morepreferably 1° C. to 25° C. When the temperature used in the treatment ofincreasing the number of the carbonate particle is less than −10° C., acarbonate formed in a needle-like shape or a rod-shape cannot beobtained, and a spherically shaped or an ellipsoid-shaped carbonate maybe yielded. When the temperature is more than 40° C., a carbonate havinga shape of an aspect ratio greater than 2 within a nanometer size regionmay not be yielded due to oversized primary particles.

The addition rate is not particularly limited and may be suitablyadjusted in accordance with the intended use. Specifically, the additionrate is preferably 0.01 mL/min to 500 mL/min, and more preferably 0.01mL/min to 100 mL/min.

—Treatment of Increasing the Volume of Carbonate Particle—

The treatment of increasing the volume of the carbonate particle is notparticularly limited and may be suitably selected in accordance with theintended use as long as the volume of the carbonate particle can beincreased without increasing the number of the carbonate particles.Examples thereof include a method in which at least any one of a metalion source and a carbonate source is added to and mixed with the othersource under the condition of a reaction temperature higher than thatused in the treatment of increasing the number of the carbonateparticles and at an addition rate faster than that used in the treatmentof increasing the number of the carbonate particles. The term “withoutincreasing the number of the carbonate particle” in the treatment ofincreasing the volume of the carbonate particle means that the number ofcarbonate particles upon completion of the treatment of increasing thevolume of the carbonate particle is increased not over 40% of the numberof carbonate particles upon completion of the treatment of increasingthe number of the carbonate particle. The number of carbonate particlesupon completion of the treatment of increasing the volume of thecarbonate particle is preferably increased not over 30%, and morepreferably, not over 20% of the number of carbonate particles uponcompletion of the treatment of increasing the number of the carbonateparticle.

Examples of the addition and mixing methods include a method in whichany one of the aqueous solution containing the carbonate source or a gascontaining the carbonate source is added to and mixed with the metal ionsource under the conditions of a reaction temperature higher than thatused in the treatment of increasing the number of the carbonate particleand an addition rate faster than that used in the treatment ofincreasing the number of the carbonate particle.

The reaction temperature is preferably 1° C. to 60° C., and morepreferably 1° C. to 55° C. When the reaction temperature is lower than1° C., handling of formed particles may be troublesome because a solventto be used is subjected to restraints. When the reaction temperature ishigher than 60° C., a solvent other than water may be evaporated.

The addition rate is not particularly limited and may be suitablyadjusted in accordance with the intended use as long as it is faster theaddition rate used in the treatment of increasing the number of thecarbonate particle. For example, the addition rate is preferably 0.1mL/min to 100 mL/min, and more preferably 0.1 mL/min to 50 mL/min. Whenthe addition rate is slower than the addition rate in the treatment ofincreasing the number of the carbonate particle, the shape of theobtained aspect ratio may not be controlled.

—pH—

The pH of a liquid in which the metal ion source is reacted with thecarbonate source is preferably in an alkali atmosphere in terms that aneedle-like or a rod-like shaped carbonate crystal is easily obtainable.Specifically, the pH of the liquid is preferably 9 or more, and morepreferably 9.5 or more. When the pH of the liquid is less than 9, thetransparency of a resin to which the carbonate crystal of the presentinvention is added may be lowered.

When the metal ion source contains an OH group, it is preferable to keepthe pH of the liquid from the start of reaction to the reaction end.When the metal ion source does not contain an OH group, it is preferredthat an agent for forming an alkali atmosphere such as NaOH is added toa liquid such that the pH of the liquid is within the above-noted range,and then reaction is performed.

—Concentration of Metal Ion Source and Carbonate Source in Reaction—

The metal ion concentration in the metal ion source and the carbonicacid ion concentration in the carbonate source used in the reaction arenot particularly limited and may be suitably adjusted in accordance withthe intended use, however, the metal ion concentration in the metal ionsource is preferably 0.05 mol/L or more, and more preferably 0.10 mol/Lor more from the perspective of reactivity.

—Other Processes—

When the metal ion source is reacted with the carbonate source, it ispreferable to react them in the presence of an organic solvent.

The organic solvent is not particularly limited and may be suitablyselected in accordance with the intended use. Examples of the organicsolvent include methanol, ethanol, 1-propanol, isopropyl alcohol,2-aminoethanol, 2-methoxy ethanol, acetone, tetrahydrofuran,1,4-dioxane, N,N-dimethylformamide, N,N-dimethylacetoamide,N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidone, anddimethylsulfoxide. Each of these may be used alone or in combination oftwo or more. Of these, the alcohols are preferably used. From theperspective of reactivity and easy availability of materials, methanol,ethanol, isopropyl alcohol, and 2-aminoethanol are more preferably used.

The content of the solvent is preferably 1% by volume to 80% by volume,and more preferably 20% by volume to 80% by volume, relative to anamount of a solvent after the carbonate is produced.

—Treatment of Removing Adsorbate—

Before carbonate crystals obtained by reacting the metal ion source withthe carbonate source is dried in a subsequent dry process, it ispreferable to remove adsorbates from surfaces of carbonate crystalparticles. In the process of producing carbonate crystals, ions derivedfrom the starting materials used in preparing particles and reactionby-products and the like are adsorbed on surfaces of the carbonatecrystal particles in liquid, and may often affect interaction betweenparticles, such as changes in electrostatic repulsive forces, andflocculation of particles in liquid is inconveniently accelerated.Drying the carbonate crystals in such a condition only gives rise toflocculated carbonate particles. As a result, even if the flocculatedparticles are added to the resin, the flocculated particles cannot bedispersed, and thus the flocculated carbonate crystal particles may besometimes contained in the resin.

The method of removing adsorbates is not particularly limited, and amethod of separating and removing unnecessary components from a particlesurface may be suitably selected in accordance with the intended use.Examples thereof include a method that includes the steps of adding purewater to the carbonate crystal particles, sufficiently stirring themixture, allowing the mixture to stand, and washing the carbonatecrystal particles washed at least once by decantation; and a method inwhich a liquid containing carbonate crystal particles is subjected toultrafiltration at least once using a function-separated polymermembrane. It is preferable to perform at least one of these methods. Theextent of removing the adsorbates can be determined by measuring theconductivity of a supernatant obtained by decantation or a filtrateobtained by ultrafiltration. The supernatant or the filtrate has aconductivity of preferably 100 μS/cm or less, and more preferably 50μS/cm or less. When the optical resin composition is produced usingcarbonate particles obtained from the supernatant or the filtrate havinga conductivity of greater than 100 μS/cm, foaming may be observed inkneading.

The function-separated polymer membrane is not particularly limited andmay be suitably selected in accordance with the intended use. Preferredexamples thereof include ion exchange resins such as strongly basic orweakly basic anionic exchange resins, strongly acidic or weakly acidiccationic exchange resins, porous ion exchange resins having a large meshstructure, and chelate resins. Preferred examples of thefunction-separated polymer membrane include reverse osmosis membranes(such as a cellulose acetate membrane, a cellulose triacetate membrane,a polypiperazine amide membrane, a all aromatic polyamide membranes, apolybenzimidazolone membrane, a crosslinked polyether membrane, analkylallylpolyamide-polyurea membrane, a polyacrylonitrile membrane, anda sulfone polysulfone membrane); microfiltration membranes (such as aacetylcellulose membrane, a polypropylene membrane, a polyvinyl chloridemembrane, a polyvinyl alcohol membrane, a polyester membrane, apolyamide membrane, and a polyimide membrane); ultrafiltration membranes(such as a cellulose membrane, a cellulose/reproduced cellulosemembrane, a polyimide membrane, a polysulfone membrane, a polyamidemembrane, a polyvinyl chloride membrane, a polypropylene membrane, and apolyvinylidene chloride; a flat membrane, a tube-like membrane, a hollowfiber membrane, a spiral membrane, and a pleated membrane may be used);dialysis membranes (a cellulose membrane, an acrylonitrile-based hollowfiber membrane, an ethylene/vinyl alcohol copolymer hollow fibermembrane, a polymethyl methacrylate membrane, a hollow fiber membrane, apolysulfone hollow fiber membrane, a polypropylene hollow fibermembrane, and a reproduced cellulose membrane); and ion exchangemembranes used in electrodialysis (an inorganic ion exchange membrane, asulfonated styrene/divinyl benzene crosslinked polymer membrane, anaminated chloromethylstyrene/divinyl benzene crosslinked polymermembrane, a N-methylated vinylpyridine/divinyl benzene crosslinkedpolymer membrane, a perfluorocarbon-based carboxylic acid membrane, anda styrene/butadiene membrane). Of these function-separated membranes,the ultrafiltration membranes or the dialysis membranes are morepreferable. The molecular mass cut off of the ultrafiltration membraneor the dialysis membrane which is preferably used in the presentinvention is not particularly limited as long as the effect of thepresent invention can be exerted. However, the molecular mass cut off istypically about 3,000 to 50,000.

These materials are described in detain in Chapters of 16th and 17th of“Functional Polymer Materials, Products and Market Ver. 1994” (issued byTokyo Techno Brain). These products are available from, as ion exchangeresins, Rohm & Haas Japan K.K. (Amber Light, Duo Light), Dow ChemicalCo. (Dow X) etc.; as ion exchange films, Asahi Kasei Corporation(Asiplex), Asahi Glass Co. (Celemion), Tokuyama Sotatsu K.K. (Neocepta),DUPONT (Nafion) etc.; as microfiltration membranes, FUJIFILM Corporation(Microfilter) etc.; as ultrafiltration membranes, Asahi KaseiCorporation (Microza UF Lab module), KURARAY Co. Ltd. (MU), DAICELCHEMICAL INDUSTRIES, LTD. (MOLSEP) etc.; as reverse osmasis membranes,Toray Industries, Inc. (PEC-1000), DNV Japan (NTR7250), DUPONT (B9, andB10) etc.: and as dialysis membranes, Sanko Junyaku Co. (dialysismembranes, cellulose tubes, manufactured by VISKASE).

—Dry Treatment—

The carbonate crystal that has been subjected to the treatment ofremoving an adsorbate is preferably subjected to a dry treatment.

The method for drying the carbonate crystal is not particularly limitedand may be suitably selected. Examples thereof include a filtration.

—Application—

According to the process of producing a carbonate crystal, a carbonatehaving a predetermined specific surface area, an orientationbirefringence, and a large aspect ratio can be efficiently and simplyformed without having flocculation of particles because the adsorbate onparticle surfaces have been removed.

—Process of Dispersing Carbonate Crystal—

A process of dispersing a carbonate crystal includes a treatment ofdispersing the carbonate crystal of the present invention in the resinand further includes other treatments suitably selected in accordancewith the intended use.

A method for dispersing a carbonate crystal in the resin is notparticularly limited and may be suitably selected in accordance with theintended use as long as the objects of the present invention can beachieved. For example, the carbonate crystals may be dispersed into theresin by kneading the carbonate crystals with the resin, or when theresin is subjected to a polycondensation reaction so as to synthesizethe resin, the carbonate crystal may be added and dispersed into theresin before completion of the polycondensation reaction. Thetemperature at which the carbonate crystal particles are dispersed inthe resin by kneading depends on the resin to be used. When the resinmainly contains polycarbonate, the dispersion temperature is preferably200° C. to 290° C., and more preferably 220° C. to 280° C. When thedispersion temperature is less than 200° C., the carbonate may not bemixed with the resin. When the dispersion temperature is more than 290°C., the physical properties of the resin may be greatly changed.

A method for molding a resin composition in which carbonate crystals aredispersed is not particularly limited and may be suitably selected inaccordance with the intended use. Examples thereof include an injectionmolding, press molding and extrusion molding. These molding methods maybe used alone or in combination of two or more. The form of the obtainedmolded article is not particularly limited and may be suitably selectedin accordance with the intended use. Examples thereof include a planeshape such as a sheet shape and film shape, an indeterminate form ofsolid such as a columnar shape, and a block shape.

The temperature for the injection molding depends on a resin to be used.When a resin mainly contains polycarbonate, the temperature of theinjection molding is preferably 150° C. to 270° C., more preferably 150°C. to 240° C. When the temperature of the injection molding is less than150° C., or more than 270° C., a desired molded article may not beobtained.

The temperature and pressure for the press molding are preferably 150°C. to 240° C. and 15 MPa to 45 MPa, more preferably 160° C. to 230° C.and 10 MPa to 40 MPa, respectively. When the molding temperature is lessthan 150° C., a desired film thickness cannot be obtained by the pressmolding. When the temperature is more than 240° C., a film-shaped maynot be obtained. When the molding pressure is less than 10 MPa, adesired film thickness may not be obtained by the press molding. Whenthe pressure is more than 40 Mpa, the resin composition may not beadjusted to a desired film thickness, however, it also depends on aspacer for adjusting a film thickness.

Alternatively, a sheet may be produced by means of the injection moldingat low cost, in which molded bodies can be obtained continuously byinjecting the resin composition without a mold. The temperature of theinjection molding is preferably 220° C. to 280° C., and more preferably230° C. to 270° C. When the temperature of the injection molding is lessthan 220° C., the resin may be stabilized and not be injected. When thetemperature of the injection molding is more than 280° C., a filmsurface may not be satisfactorily obtained.

A method for aligning molecules in a molded sheet is not particularlylimited and may be suitably selected in accordance with the intended useas long as the objects of the present invention can be achieved.Examples there of include a uniaxial drawing method and biaxial drawingmethod. The biaxial drawing method can longitudinally and laterally drawthe molded sheet in sequence or at the same time. The molded sheet maybe drawn after it has been cut in a predetermined size; alternatively,the molded sheet may be molded and then sent to a drawing device fordrawing.

A film of the optical resin composition can be obtained by drawing a 100μm-thick sheet, which is drawn to 2 times the original size by theinjection molding or press molding, at 165° C. and at a speed of 3mm/min by a biaxial drawing device. Alternatively, a sheet obtained bythe injection molding can be consecutively drawn to 2 times the originalsize at 165° C. and at a speed of 3 mm/min by a biaxial drawing device.

EXAMPLES

Hereinafter, Examples of the present invention will be explained, butthe present invention is not limited thereto.

Example 1 Production of Carbonate Crystal

As shown in FIG. 2, carbonate was produced by means of the single-jetmethod.

—Treatment of Increasing the Number of Carbonate Particle—

375 mL (75 ml of water, 300 ml of methanol) of a 0.08 mol/L strontiumhydroxide [Sr(OH)₂] suspension which had been prepared from strontiumhydroxide octahydrate as a metallic ion source in a stainless-steel potwas taken as Liquid A. While, 500 mL of a 0.2 mol/L ammonium carbonate[(NH₄)₂CO₃] aqueous solution as a carbonate source was taken as Liquid.B, Liquid B was then poured into two feed tanks separately, and thetemperature was maintained at 10° C. While stirring Liquid A at 1,000rpm with the temperature maintained at 10° C., 62.5 mL of Liquid B ineach of the two feed tanks was respectively added to Liquid A in thestainless-steel pot at an addition rate of 0.5 mL/min and then mixed.

—Treatment of Increasing the Volume of Carbonate Particle—

Next, 250 mL of a 0.1 mol/L strontium hydroxide [Sr(OH)₂] suspension

(Liquid A) was poured into the mixture of Liquid A and Liquid B whilestirring Liquid A at 1,000 rpm with the temperature raised to 50° C.,and then 250 mL of a 0.1 mol/L ammonium carbonate [(NH₄)₂CO₃] aqueoussolution was slowly added thereto at an addition rate of 1 mL/min.

—Treatment of Removing Adsorbate—

A cycle of adding 1 liter of pure water to the mixed liquid, allowingthe mixture to stand, and removing the water by decantation was repeateduntil the supernatant had a conductivity of 52 μS/cm.

To the liquid, PLENACT KR44, manufactured by Ajinomoto Fine-Techno Co.,Ltd., was added to a concentration of 3% by mass relative to a generatedsediment, and was sufficiently stirred for surface treatment.

—Drying Process—

Finally, the obtained sediment in the liquid was subjected to suctionfiltration using a Buchner funnel, and a cake was dried at 150° C. for 2hours to obtain a white dry powder.

—Evaluation of Carbonate—

The dried powder was measured using an X-ray diffractometer, and themeasurement result showed that the powder was comprised of strontiumcarbonate crystals. Further, the strontium carbonate crystals wereobserved using a transmission electron microscope (TEM). From a TEMpicture of particles, a particle size, aspect ratio, variationcoefficient obtained from Formula (1) were found. The variationcoefficient was obtained by measuring each of the particles in an imagefile using image analysis type of particle distribution measuringsoftware “Mac-View” Ver. 3 (manufactured by MOUNTECH Co., Ltd.) andcounting the measured values. The specific surface area was measuredusing an automatic specific surface area/micropore distribution analyzer(BELSORP-mini, manufactured by BEL JAPAN Inc.). The strontium carbonatecrystals were heated at 200° C. for pretreatment. The results are shownin Table 3.

—Process of Dispersing Carbonate Crystal and Evaluation of Optical ResinComposition—

The obtained carbonate particles and polycarbonate resins were kneadedat 220° C. by a small kneader, so that the content of the carbonateparticles was 1% by mass relative to the resin, thereby obtained acomposite resin in a form of a pellet. The resin was injection molded at220° C., and a sheet having a thickness of 100 μm was produced by pressmolding at 220° C./30 MPa as an optical resin composition. At this step,the light transmittance of the composition was measured and itsdispersibility was evaluated by SEM. Moreover, the 100 μm-thick sheetwas cut out in a size of 55 mm×30 mm, and was uniaxially drawn to 1.5times the original size at 165° C. and at a speed of 3 mm/min by abiaxial drawing device by Imoto seisakusho to obtain an optical resincomposition having a thickness of 68 μm. The results are shown in Table3.

Example 2

A treatment of increasing the number of carbonate particles wasconducted as in Example 1 except that 375 mL of the suspension of LiquidA (50 ml of water, 325 ml of methanol) was maintained at 5° C., andLiquid B was added at an addition rate of 0.3 mL/min.

A treatment of increasing the volume of carbonate particles wasconducted as in Example 1 except that 250 mL of an ammonium carbonate[(NH₄)₂CO₃] aqueous solution was added at an addition rate of 0.5mL/min.

A treatment of removing adsorbates from particle surfaces was conductedby subjecting the mixed liquid to ultrafiltration by means of Microza UFLab module (by Asahi Kasei Chemicals) made of polysulfone and having amolecular mass cut off of 6,000 until a filtrate had a conductivity of28.6 μS/cm.

Finally, a cake was dried at 150° C. for 2 hours to obtain a white drypowder. The obtained carbonate crystal and optical resin compositionwere evaluated in the same manner as in Example 1. The results are shownin Table 3.

Example 3

A treatment of increasing the number of carbonate particles wasconducted as in Example 2 except that Liquid B was added at an additionrate of 0.4 mL/min.

A treatment of increasing the volume of carbonate particles wasconducted as in Example 2 except that 250 mL of an ammonium carbonate[(NH₄)₂CO₃] aqueous solution was added at an addition rate of 0.7mL/min.

The adsorbates on particle surfaces were removed by subjecting the mixedliquid to ultrafiltration until a filtrate had a conductivity of 27.2μS/cm.

Finally, a cake was dried at 150° C. for 2 hours to obtain a white drypowder. The obtained carbonate crystal and optical resin compositionwere evaluated in the same manner as in Example 1. The results are shownin Table 3.

Example 4

The carbonate crystal and optical resin composition were evaluated inthe same manner as in Example 3 except that a calcium hydroxidesuspension was used instead of the strontium hydroxide suspension ofLiquid A in Example 3. The results are shown in Table 3.

Example 5

The carbonate crystal and optical resin composition were evaluated inthe same manner as in Example 3 except that a barium hydroxidesuspension was used instead of the strontium hydroxide suspension ofLiquid A in Example 3. The results are shown in Table 3.

Example 6

The carbonate crystal and optical resin composition were evaluated inthe same manner as in Example 3 except that a zinc hydroxide suspensionwas used instead of the strontium hydroxide suspension of Liquid A inExample 3. The results are shown in Table 3.

Example 7

The carbonate crystal and optical resin composition were evaluated inthe same manner as in Example 3, except that a lead hydroxide suspensionwas used instead of the strontium hydroxide suspension of Liquid A inExample 3. The results are shown in Table 3.

Example 8

A treatment of increasing the number of carbonate particles wasconducted as in Example 1 except that 375 mL of the suspension of LiquidA (50 ml of water, 325 ml of methanol) was maintained at 3° C. and, thatLiquid B was added at an addition rate of 0.1 mL/min.

A treatment of increasing the volume of carbonate particles wasconducted as in Example 1 except that the temperature was raised to 45°C. and that 250 mL of an ammonium carbonate [(NH₄)₂CO₃] aqueous solutionwas added at an addition rate of 0.4 mL/min.

The adsorbates on particle surfaces were removed by subjecting the mixedliquid to decantation continuously until a filtrate had a conductivityof 28.6 μS/cm.

Finally, a cake was dried at 150° C. for 2 hours to obtain a white drypowder. The obtained carbonate crystal and optical resin compositionwere evaluated in the same manner as in Example 1. The results are shownin Table 3.

Example 9

The carbonate crystal and optical resin composition were evaluated inthe same manner as in Example 8 except that the temperature of thetreatment of increasing the number of the carbonate particle was changedto 5° C. The results are shown in Table 3.

Example 10

The carbonate crystal and optical resin composition were evaluated inthe same manner as in Example 9 except that the temperature ofincreasing the volume of the carbonate particle was changed to 47° C.The results are shown in Table 3.

Comparative Example 1

The carbonate crystal and optical resin composition were evaluated inthe same manner as in Example 1 except that the content of the obtainedcarbonate particles was changed to 17% by mass relative to resin inExample 1.

Comparative Example 2

The carbonate crystal and optical resin composition were evaluated inthe same manner as in Example 1 except that decantation was notperformed and the obtained sediment in the liquid was subjected tosuction filtration using a Buchner funnel in Example 1. A filtrate had aconductivity of 9,735 μS/cm. The results are shown in Table 3.

Comparative Example 3

250 mL (250 ml of water) of a 0.05 mold, strontium hydroxide [Sr(OH)₂]suspension which had been prepared from strontium hydroxide octahydrateas a metallic ion source in a stainless-steel pot was taken as Liquid A,and a 4.00 g of sodium hydroxide granulated powder was dissolved inLiquid A. While 500 mL of a 4 mol/L urea [(NH₂)₂CO] aqueous solution wastaken as Liquid B. While stirring Liquid A at 1,000 rpm with atemperature raised and maintained at 90° C., 500 mL of Liquid B waspoured into one feed tank and added to Liquid A in the stainless-steelpot at an addition rate of 250 mL/min and then mixed. A cycle of adding1 liter of pure water to the mixed liquid, allowing the mixture tostand, and removing the water by decantation was repeated until asupernatant having a conductivity of 84 μS/cm was obtained. Finally, acake was dried at 150° C. for 2 hours to obtain a white dry powder.

The obtained carbonate crystal and optical resin composition wereevaluated in the same manner as in Example 1. The results are shown inTable 3.

Comparative Example 4

Only a polycarbonate resin was kneaded at 220° C. by a small kneader toobtain a resin in a form of pellet. The resin was injection molded at220° C., and a sheet having a thickness of 100 μm was prepared by pressmolding at 220° C./30 MPa as an optical resin composition. At this step,the light transmittance of the composition was measured. A 100 μm-thicksheet was cut out in a size of 55 mm×30 mm, and was uniaxially drawn to1.5 times the original size at 165° C. and at a speed of 3 mm/min by abiaxial drawing device by Imoto seisakusho to obtain an optical resincomposition having a thickness of 68 μm. The results are shown in Table3.

TABLE 3 Average of Variation specific surface Aspect maximum coefficientAdded area *1) ratio major axis represented by Composition amount [m²/g][—] lengths [nm] Formula (1) [%] of particles [%] Ex. 1 11 4.2 395 31SrCO₃ 1 Ex. 2 15 4 267 38 SrCO₃ 1 Ex. 3 4 3.8 315 35 SrCO₃ 1 Ex. 4 4 3.4363 40 CaCO₃ 1 Ex. 5 6 4.8 343 32 BaCO₃ 1 Ex. 6 8 4.4 345 28 ZnCO₃ 1 Ex.7 10 3.9 334 33 PbCO₃ 1 Ex. 8 4 4 150 30 SrCO₃ 1 Ex. 9 4 4.4 300 25SrCO₃ 1 Ex. 10 4 4.1 350 15 SrCO₃ 1 Comp. Ex. 1 11 4.2 395 31 SrCO₃ 17Comp. Ex. 2 11 3.7 415 45 SrCO₃ 1 Comp. Ex. 3 3.5 23.5 27000  23 SrCO₃ 1Comp. Ex. 4 — — — — — 0 Light Average transmit- dispersion Birefringencetance *2) diameter Dispersion Conductivity index *4) Form [%] [nm]Condition *3) [μS/cm] [—] Ex. 1 film 88.2 450 A 52 1 × 10⁻⁴ Ex. 2 film89.4 387 A 28.6 1 × 10⁻⁴ Ex. 3 film 86.5 410 A 27.2 3 × 10⁻⁴ Ex. 4 film86.9 436 A 43 6 × 10⁻⁴ Ex. 5 film 88 420 A 56 5 × 10⁻⁴ Ex. 6 film 87.8487 A 42 2 × 10⁻⁴ Ex. 7 film 88.1 431 A 50 4 × 10⁻⁴ Ex. 8 film 89 290 A26.7 4 × 10⁻⁵ Ex. 9 film 88 438 A 45 8 × 10⁻⁵ Ex. 10 film 88.2 473 A 501 × 10⁻⁴ Comp. Ex. 1 film 43.8 1248 C 52 Not measured Comp. Ex. 2 film72.1 1912 C 9,735 Not measured Comp. Ex. 3 film 35.4 34.1 A 84 4 × 10⁻⁴Comp. Ex. 4 film 91.3 — — — 1 × 10⁻³ *1) Values for dry power beforemixed with resin. *2) Values for light transmittance at a wavelength of450 nm in a sheet standardized to 100 μm-thick. *3) The dispersioncondition was evaluated by SEM observation. A: Excellent dispersion, B:Some amount of flocculation existed, C: Severe flocculation *4) Valuesof birefringence obtained by measuring a retardation at a wavelength 550± 5 nm by Automatic Birefringence Analyzer (KOBRA-21ADH, manufactured byOji Scientific Instruments Co., Ltd.), and then dividing with a filmthickness.

From the results of Table 3, it is understood that the optical resincompositions of Examples 1 and 2 in which dispersed carbonate crystalsare contained have high light transmittance at a wavelength of 450 nmcompared to Comparative Examples 1 to 3, and that birefringence indexcan be changed in contrast to Comparative Examples 1 to 3.

Example 11

A polyethylene terephthalate resin composition containing a strontiumcarbonate crystal was obtained by adding 1% by mass of the strontiumcarbonate crystal prepared in Example 1 in a polycondensation reactionof terephthalic acid and ethylene glycol. The transmittance andbirefringence after the drawing process for each of the obtainedpolyethylene terephthalate resin compositions were measured in the samemanner as in Example 1, and it was confirmed that those are comparablewith those measured in Example 1.

It was also confirmed that similar effects were obtained withpolyethylene naphthalate resin compositions and triacetylcellulose resincompositions.

An optical resin composition containing the carbonate crystal of thepresent invention is able to negate the birefringence withoutsacrificing light transmittance; therefore, it may be preferably used asa resin material that constitutes an optical component, particularlyoptical elements with which birefringent properties is important andhigh precision is required.

A method for producing an optical resin composition according to thepresent invention may easily and efficiently produce a carbonate crystalhaving a predetermined specific surface area, an oriented birefringenceand high aspect ratio without having flocculation of particles becauseadsorbates on particle surfaces have been removed, and may be suitablyused to produce an optical resin composition of the present invention.

1. An optical resin composition comprising: a resin; and carbonatecrystals having a specific surface area of 4 m²/g or more, wherein thecarbonate crystals dispersed into the resin have an average dispersiondiameter of 500 nm at a maximum.
 2. The optical resin compositionaccording to claim 1, wherein the optical resin composition has a lighttransmittance of 86% or greater at a wavelength of 450 nm.
 3. Theoptical resin composition according to claim 1, wherein the content ofthe carbonate crystals relative to the resin is 0.01% by mass to 15.00%by mass.
 4. The optical resin composition according to claim 1, whereinthe resin is any one selected from a cellulose acylate resin, apolyethylene terephthalate resin, a polyethylene naphthalate resin and apolycarbonate resin.
 5. The optical resin composition according to claim1, wherein the carbonate crystals have an aspect ratio of 2 or greater,an average major axis length of 400 nm or shorter, and a variationcoefficient of the major axis expressed by Formula (1) of 0.40 or less:$\begin{matrix}{\frac{1}{r} \times \left\{ {\frac{1}{n - 1}{\sum\limits_{i = 1}^{n}\left( {r_{i} - r} \right)^{2}}} \right\}^{\frac{1}{2}}} & {{Formula}\mspace{14mu} (1)}\end{matrix}$ wherein r denotes an average major axis length, n denotesthe number of particles whose major axis length is measured, and r_(i)denotes the major axis length of the i^(th) particle measured.
 6. Amethod for producing an optical resin composition comprising: producingcarbonate crystals, and dispersing the produced carbonate crystals intoa resin, wherein the step of producing carbonate crystals comprisesreacting a metal ion source that contains at least one metal ionselected from Sr²⁺, Ca²⁺, Ba²⁺, Zn²⁺ and Pb²⁺ with a carbonate source inliquid.
 7. The method for producing an optical resin compositionaccording to claim 6, wherein the carbonate crystals have a specificsurface area of 4 m²/g or more, and the carbonate crystals dispersedinto the resin have an average dispersion diameter of 500 nm at amaximum.
 8. The method for producing an optical resin compositionaccording to claim 6, wherein the step of producing carbonate crystalscomprises removing an adsorbate from surfaces of the carbonate crystals.9. The method for producing an optical resin composition according toclaim 8, wherein the step of removing an adsorbate comprises any one ofa method for washing the carbonate crystal at least once by decantationand a method for subjecting the carbonate crystal to ultrafiltration atleast once.
 10. The method for producing an optical resin compositionaccording to claim 9, wherein a supernatant obtained by the decantationor a filtrate obtained by the ultrafiltration has a conductivity of 100μS/cm or less.
 11. The method for producing an optical resin compositionaccording to claim 6, wherein the step of producing carbonate crystalscomprises increasing, at least once, the number of the carbonate crystalin liquid, and increasing, at least once, only the volume of thecarbonate crystals in liquid.
 12. The method for producing an opticalresin composition according to claim 11, wherein the temperature of thestep of increasing the number of the carbonate crystals is −10° C. to40° C., and a temperature of the step of increasing the volume of thecarbonate crystal is 1° C. to 60° C. and not less than the temperatureof the step of increasing the number of the carbonate particles.
 13. Themethod for producing an optical resin composition according to claim 6,wherein the step of dispersing the carbonate crystals into the resincomprises dispersing the carbonate crystal into the resin by kneading.14. The method for producing an optical resin composition according toclaim 13, wherein a method for molding the optical resin composition inwhich the carbonate crystal is dispersed is any one of an injectionmolding, press molding and extrusion molding.